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Sulfinylnitriles: Sulfinyl–Metal Exchange–Alkylation Strategies

Authors

  • Dinesh Nath,

    1. Department of Chemistry and Biochemistry, Duquesne University, 600 Forbes Ave, Pittsburgh PA 15282 (USA), Fax: (+1) 412-396-5683
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  • Prof. Fraser F. Fleming

    Corresponding author
    1. Department of Chemistry and Biochemistry, Duquesne University, 600 Forbes Ave, Pittsburgh PA 15282 (USA), Fax: (+1) 412-396-5683
    • Department of Chemistry and Biochemistry, Duquesne University, 600 Forbes Ave, Pittsburgh PA 15282 (USA), Fax: (+1) 412-396-5683
    Search for more papers by this author

Abstract

Adding organolithiums, Grignard reagents, or zincates to sulfinylnitriles triggers a facile sulfinyl–metal exchange to afford N- or C-metalated nitriles. Sulfinyl–magnesium exchange–alkylations efficiently install quaternary and tertiary centers, even in the case of tertiary sulfinylnitriles that contain a highly acidic methine proton. α-Sulfinylalkenenitriles afford moderately nucleophilic magnesiated nitriles, and the reactivity can be dramatically increased by conversion to the corresponding magnesiates. The sulfinyl-metal exchange is extremely fast, proceeds efficiently with quaternary, tertiary, and vinylic α-sulfinylnitriles, and exhibits an exceptional functional group tolerance in nitrile alkylations.

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